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Process for synthesis of aluminum coordinations compounds

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US4767875A
US4767875A US06762084 US76208485A US4767875A US 4767875 A US4767875 A US 4767875A US 06762084 US06762084 US 06762084 US 76208485 A US76208485 A US 76208485A US 4767875 A US4767875 A US 4767875A
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Paul J. Vincenti
James D. Warren
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Procter and Gamble Co
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Wyeth Holdings Corp
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/68Preparation of metal alcoholates
    • C07C29/70Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/28Metal alcoholates
    • C07C31/32Aluminium alcoholates
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06Aluminium compounds
    • C07F5/069Aluminium compounds without C-aluminium linkages
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/58Metal complex; Coordination compounds

Abstract

A method for producing heterocyclic aluminum compounds of the formula: ##STR1## where n is 0 to 1, by reacting aluminum chloride with an aliphatic polyhydric alcohol having from 2 to 6 carbon atoms and having hydrogen, hydroxy, or low alkyl groups on carbon atoms which are spaced apart by no more than one intervening carbon atom, which is useful as an anti-perspirant.

Description

The present invention relates to heterocyclic organic aluminum compounds and to methods for their preparation. The compounds of the present invention are particularly useful for anti-perspirants.

The requirements for anti-perspirant compositions are quite rigorous. The anti-perspirant compositions must form homogenous systems in both fluid and solid form. They must be stable for reasonable storage periods. They should contain only trace amounts of iron, since this metal inactivates compounds such as "hexachlorophene" and also catalyzes degradation of some organic perfume materials. The anti-perspirant compositions should have a low acidity pH range on the order of 3.5 to 4.5 when mixed with water. They must be sufficiently soluble to be effective and they must be safe to use daily on the skin. Most important, they must be effective in inhbiting the flow of perspiration on the axillae.

Aluminum chloride hexahydrate has been used as an anti-perspirant composition for a long period of time. Although it is compatible with anhydrous ethanol, and compatible with propellants, and is an effective anhydrotic, it is too acid to use daily, and has adversely affected the tensile strength of fabrics. Less acid materials such as aluminum phenolsulphonate have been used as anti-perspirant composition, but the anti-perspirant activity of these materials is quite low. The patent literature also includes a disclosure of aluminum chlorhydroxide alcoholate having 0.25 to 1 hydroxyl for each aluminum atom in anti-perspirant compositions (U.S. Pat. No. 2,823,169). These materials, however, are rather unstable and they contain more than a trace amount of iron, usually including on the order of 40 to 80 parts per million of iron. U.S. Pat. No. 2,872,379 discloses a series of alkoxy aluminum chlorides as anti-perspirants, but these compounds are limited in usefulness because of their very low solubility in anhydrous alcohol. Such a group of compounds are described in U.S. Pat. No. 3,444,292, and are cyclic organo-aluminum compounds.

An object of the present invention is to provide an improved process for preparing organo-aluminum compounds useful as antiperspirants. This and other objects will become apparent as the description of the invention proceeds.

The compounds produced in the process of the present invention have the following generic formula: ##STR2## where n is an integer from 0 to 1.

As indicated in the above structural formula, the heterocyclic compounds of the present invention include a ring structure which may number from 5 to 6 atoms in the ring. The linkage: ##STR3## forming part of the above identified structural formula is preferably a residue of an aliphatic polyhydric alcohol having from 2 to 6 carbon atoms per molecule and having hydroxyl atoms on carbon atoms which are spaced apart by no more than one intervening carbon atom.

The valance bonds shown in the above structural formula should be attached to groups which do not have an adverse effect upon the solubility or the acidity of the resulting compound, and should preferably be either hydrogen atoms, hydroxyl groups, or low alkyl chains (up to 3 carbon atoms).

The above described compounds are produced, in the process of the present invention, by reacting aluminum chloride with an aliphatic polyhydric alcohol having from 2 to 6 carbon atoms and having carboxyl groups of carbon atoms which are spaced apart by no more than one intervening carbon atom.

This basic reaction was described and claimed in copending, commonly assigned application Ser. No. (Case 29,357), filed Aug. 2, 1985. In the copending application, the reaction was conducted in the presence of diethyl ether for about five hours, at room temperature, the product was washed with diethyl ethers, dried under vacuum, at room temperature suspended in diethyl ether, filtered, rinsed with diethyl ether and again dried under vacuum at room temperature. It was found that the product contained residual hydrogen chloride and diethyl ether and this made the product less satisfactory when applied to the skin for use in an antiperspirant composition.

The present process is described generally as follows: ##STR4## The reaction as stated provides the diol complexes in good yield, but is complicated by the moisture sensitivity of the product. Even under strict conditions (freshly distilled ether, anhydrous AlCl3, 99+% propylene glycol, all under a nitrogen atmospher) the water content of the product was measured at 10%. With this amount of water present, the following hydrolysis most likely takes place: ##STR5## followed by a secondary hydrolysis of the hexaaquoaluminum ion. The final result of that hydrolysis is intimately connected to the pH of the system:

Al(H.sub.2 O).sub.6.sup.3.spsp. +OH.sup.- →Al(OH).sub.x (H.sub.2 O).sub.y

Therefore, a proper representation of the product is a mixture of the original diol complex, water, and hydrolysis products. Since this process provides material which is of commercial interest in its present form, more costly and complicated purification methods would not be feasible in our process. Also, constraints that we could practice in a laboratory environment would be unsuitable for production level of this material. A final purity of 80-85% is probably a good estimate when moisture and hydrolysis products are taken into account.

Suitable solvents are organic solvents having a dielectric constant from about 2 to 20 and boiling at a temperature of not greater than about 100° C. such as diethyl ether and others described subsequently in Table I.

It has been found that if the final rinses and vacuum drying are eliminated, and the product is heated at elevated temperature, e.g. 90° C., for about 48 hours, a high yield of product is obtained, over 90% yield. The product is also free of residual hydrogen chloride and diethyl ether. Thus, the product is useful in compositions for application to the skin as an antiperspirant, and is highly efficacious for this purpose.

It may be desirable when use a more volatile solvent, e.g. diethyl ether, to subject the product to vacuum drying to remove some of the solvent. But this is not necessary to the process.

It was highly surprising that the final heating step could be utilized without detriment and with the beneficial results obtained.

The product of the invention is not normally ethanol soluble, but this is not a limitation since it is soluble in aqueous ethanol solutions.

The present process produces more economically and efficiently a complex which has shown marked utility in the inhibition of perspiration versus the untreated axillary area, namely a 45.4% reduction in perspiration. With respect to the previously claimed 2-Chloro-4-diethyl-1,2,3-Dioxalumolane (U.S. Pat. Nos. 3,444,226 and 3,444,292), the preparation of the present application results in a non-solvated species as well as yields in excess of 90%. The reaction utilizes readily available materials and accomplishes the reaction at room temperature rather than in refluxing isopropanol at an elevated temperature of 82° C. to 83° C.

The following specific examples illustrate preparation of the organo-aluminum complexes by the process of the present invention, and the efficaciousness of these compounds as antiperspirant compounds.

The scale of these reactions range from 2-1800 g depending on the diol used with 1,2-propanediol being the most heavily investigated. The reaction seems to be quite general with respect to diol, however, if the hydroxyl groups are separated by more than 3-4 carbon atoms, competitive reactions may result. Chelation of the two ends onto the aluminum center may be concurrent with monodentate attachment on either end of the diol. Also, other functional groups (eg. ester or ether groups) may also interact with the metal center. Finally, solvent choices seems to preclude straight chain hydrocarbons (solubility/decomposition) and/or low molecular weight alcohols (may form complexes with the aluminum reagent).

EXAMPLE I

Anhydrous aluminum chloride (75 g; 0.56 mole) was combined with 500 ml diethyl ether in a 2 liter flask which had been cooled in an ice/acetone bath. The order of addition is more important as the scale is increased. At large scale, the diethyl ether should be cooled prior to addition of the aluminum chloride to prevent decomposition of the metal halide. Such decomposition is not evident when small scale (75 g AlCl3 or less) reactions are run. Upon mechanical stirring, the metal halide completely dissolved upon addition. Dropwise addition of 1,2-propanediol (41.3 ml; 0.56 mole) resulted in the precipitation of a white solid. After stirring for 4.5 hours under nitrogen at room temperature, the white solid was filtered and washed with 400 ml diethyl ether. The product was dried under vacuum at room temperature for 15 hours. After suspending the product in diethyl ether and filtering, another 15 hours of vacuum drying at room temperature was carried out. After this time, the temperature was raised to 90° C. for an additional 48 hours. The white solid (72.2 g; 94% yield calculated in accordance with the molecular formula C3 H6 OAlCl) was stored in a desiccator over calcium sulfate.

Elemental analysis of the compound shows that the molecular unit OCH2 CH(Me)OAlCl is present. This is further verified by vapor phase osmometry in 1,2-propanediol which gives a molecular weight of 142 (136.5 calculated). Hydrolysis upon dissolution in water results in resonances for the free 1,2-propanediol ligand in the 1 H and 13 C NMR spectra.

EXAMPLE II

The reaction of the present invention was carried out with a number of diols and at varying temperature, as shown in table I.

Table I contains information on 9 diol ligands, 10 solvent variations, and reaction temperatures spanning a range of -10°-111° C. Data on reactions that did not provide the diol complex is also included. The molar ratio of aluminum and chlorine is given with the ideal ratio being equal to 1.0.

EXAMPLE III

In this Example, a number of diols were used on varying quantitative reaction scales. The results, yields and product analysis are shown in table II.

EXAMPLE IV Antiperspirant Efficacy of Propylene Glycol-Aluminum Chloride Complex vs. Aluminum Zirconium Glycine (CEL #'s 83-31 and 83-35; A/P Screening Tests)

Antiperspirant (A/P) screening test CEL 83-31 was conducted to construct a dose-response curve by evaluating A/P efficacy of various amounts of 12.6% PG-AlCl (propylene glycol-aluminum chloride, CPRD #13857); 0.5 ml Al:Zr-Gly (24%; aluminum zirconium glycine, CPRD #13384) was used as a benchmark for efficacy. Although the lowest amount of PG-AlCl (41 mg active) did not yield a sweat reduction that significantly exceeded 20%, all other amounts (≧68 mg active) did so, and were equieffective with respect to each other and the benchmark amount of Al:Zr-Gly. CEL 83-35 was conducted to supplement the data points where the two test compounds were administered on an equivalent metal basis (ca. 35 mg/application). In that investigation, Al:Zr-Gly was 26% more effective than PG-AlCl (p<0.05), but when the results of both studies were combined (N=51), the two compounds did not differ at the 90% level of confidence, with Al:Zr-Gly directionally more effective.

                                  TABLE I__________________________________________________________________________TEMPERATURE     LIGAND   SOLVENT   ANALYSIS__________________________________________________________________________-10°-25° C.     1,2-propanediol              Et.sub.2 O                        Cl/Al = 1.0-10°-40° C.     (CL 282,006)              CH.sub.2 Cl.sub.2                        Cl/Al = 1.0-18°-25° C.              THF       Cl/Al = 1.025°-82° C.              iPrOH     Cl/Al = 1.125° C.      C.sub.7 H.sub.16                        NR0°-25° C.              C.sub.4 H.sub.9 Br                        NR0°-25° C.              MeOCH.sub.2 CH.sub.2 OMe                        mixture of products0°-78° C.              EtOH      mixture of products-10°-25° C.     1,3-propanediol              Et.sub.2 O                        Al/Cl = 1.2-10°-34° C.     1,3-butanediol              Et.sub.2 O                        Cl/Al = 1.1-10°-25° C.     1,4-butanediol              Et.sub.2 O                        Cl/Al = 1.025° C.     (CL 282,012)              C.sub.6 H.sub.14                        NR-10°-34° C.     2,3-butanediol              Et.sub.2 O                        Cl/Al = 1.025°-82° C.              iPrOH     Cl/Al = 1.225°-69° C.              C.sub.6 H.sub. 14                        NR0°-82° C.     glycerol iPrOH     Al/Cl = 1.1-10°-25° C.     glycerol-1-acetate              Et.sub.2 O                        mixture of products-10°-25° C.     hexylene glycol              Et.sub.2 O                        mixture of products25°-111° C.     decylene glycol              toluene   NR25°-34° C.              Et.sub.2 O                        NR__________________________________________________________________________ NR = no reaction/decomposition

                                  TABLE II__________________________________________________________________________            Average AnalysisLIGAND/SOLVENT       SCALE            COMPLEX YIELD                       COMPLEX                              H.sub.2 O                                  IMPURITY__________________________________________________________________________PG/Et.sub.2 O       1800          g 89%        92%    4.6%                                  3.4%PG/Et.sub.2 O       800          g 92%        92%    2.8%                                  5.2%PG/CH.sub.2 Cl.sub.2       10 g 47%        80%    15%  5%PG/THF      26 g 55%        79%    7.3%                                  13.7%PG/iPrOH    5  g --         80%    12%  8%1,3-propanediol/Et.sub.2 O       5  g 66%        82%     8% 10%1,3-butanediol/Et.sub.2 O       10 g 31%        [68%]  [29%]                                   3%1,4-butanediol/Et.sub.2 O       6  g 76%        91%    5.5%                                  3.5%2,3-butanediol/Et.sub.2 O       10 g 42%        80%    10% 10%2,3-butanediol/iPrOH       27 g 18%        82%     9%  9%glycerol/iPrOH       18 g 81%        81%     2% 17%                        84%*   7.6%*                                   8.4%*__________________________________________________________________________ *w/o 1,3butanediol product impurity = excess diol and/or dydrolysis product
METHODOLOGY

Respondents. One hundred three women participated in CEL 83-31; 51 different subjects took part in CEL 83-85. In both studies, respondents refrained from antiperspirant use for a 17-day period prior to the start of the tests. They were permitted ad libitum use of OLD SPICE® Aerosol Deodorant during the conditioning period and shaved their axillae no less than three days before the test began.

Products. The treatments evaluated in these studies uses laboratory scale solutions and were applied by syringe. Details are shown in Table III:

              TABLE III______________________________________                           Amount Studies             Active and    Applied                                  Evalu-Description    CPRD #   % Conc.       (ml)   ated______________________________________A/P Solution    13857    PG--AlCl 12.6%                            0.324 83-31A/P Solution    13857    PG--AlCl 12.6%                           0.54   83-31A/P Solution    13857    PG--AlCl 12.6%                           0.90   83-31A/P Solution    13857    PG--AlCl 12.6%                           1.50   BothA/P Solution    13857    PG--AlCl 12.6%                           2.50   83-31A/P Solution    13384    Al:Zr--Gly 24.0%                           0.50   BothUntreated    --       --            --     Both______________________________________

The various amounts of CPRD 13857 applied in CEL 83-31 are equally spaced on a log scale; successive amounts increase by a factor of 1.67.

Procedure. On Days 1, 2, and 3 of 83-31, respondents washed their axillae with 3% soap under supervision; unilateral treatment with one of the five amounts of CPRD 13857 or 0.5 ml CPRD 13384 followed. Each respondent's other axilla was untreated: the left side for half and the right for the remainder. The same axilla of a given subject was treated each day. On Day 4, respondents sat in the CEL hot room for 80 minutes. Sweat output from minutes 41 through 60 and 61 through 80 was measured gravimetrically. The results of these two intervals were averaged.

The procedures were similar for CEL 83-35, but a round-robin design was employed. Respondents received two of the following treatments (one per axilla): 1.50 ml CPRD 13857, 0.50 ml CPRD 13384, or untreated. Thus, two-thirds rather than all of the respondents had an untreated axilla, with the remainder testing the two solutions head-to-head.

RESULTS

Table IV presents mean mg sweat output and percent reduction versus untreated and results of statistical analysis for CEL 83-31:

                                  TABLE IV__________________________________________________________________________Results of CEL 83-31         Amount          Mean Sweat Output                                       % Reduction vs.Treatment     Applied (ml)                 mg PG-AlCl                         (mg/20 min.)                                    N  Untreated (95%                                                   Significance*__________________________________________________________________________CPRD 13857 (PG--AlCl)          0.324   41     274        17 28.59 (3.05,                                                   a7.41)CPRD 13857 (PG--AlCl)         0.54     68     184        18 52.04 (35.47,                                                     a,b)CPRD 13857 (PG--AlCl)         0.90    113     135        17 64.85 (52.28,                                                   b4.11)CPRD 13857 (PG--AlCl)         1.50    189     153        17 59.98 (45.66,                                                   b0.52)CPRD 13857 (PG--AlCl)         2.50    315     176        17 54.01 (37.56,                                                   b6.12)CPRD 13384 (Al:Zr--Gly)         0.50    --      193        17 49.58 (31.55,                                                     a,b)Untreated     --      --      383        103                                       0           c__________________________________________________________________________ *Treatments with the same letter are not significantly different (p > .05

It can be seen in Table IV above that all treatments produced significant reductions versus untreated and that increasing tha mount of PG AlCl above 0.9 ml (113 mg active) did not result in significantly greater efficacy.

Table V below presents the corresponding data from CEL 83-35:

                                  TABLE V__________________________________________________________________________Results of CEL 83-35         Amount Mean Sweat  % Reduction vs.Treatment     Applied (ml)                Output (mg/20 min)                          N Untreated (95% C.L.)                                       Significance__________________________________________________________________________CPRD 13857 (PG--AlCl)         1.50   135       34                            63.31 (50.59, 72.75)                                       aCPRD 13384 (Al:Zr--Gly)         0.50   100       34                            72.86 (63.45, 79.85)                                       bUntreated     --     367       34                            0          c__________________________________________________________________________

Both treatments produced mean sweat reductions significantly greater than 20% (p<0.05). This direct comparison of the two actives on a "metal per application" basis indicates that the Al:Zr-Gly was more effective than the PG-AlCl, at least at 3.5 mg Al (p<0.05). Examination of the results shown in Tables IV and V revealed that whereas the sweat outputs from PG-AlCl and untreated were consistent in the two experiments, the Al:Zr-Gly was considerably more effective in CEL 83-35. The performance of the Al:Zr-Gly in this experiment is considerably better than its "track record" under comparable conditions in the CEL: a 44.1% reduction in CEL 83-13 and 57.4% in CEL 83-27. Conclusions regarding the comparative efficacy of these compounds at 3.5 mg Al should take this into account.

When the results of 83-31 and 83-35 are pooled, the advantage of Al:Zr-Gly over PG-AlCl is reduced to one of directionality, as shown in Table VI.

                                  TABLE VI__________________________________________________________________________Pooled Results of CEL 83-31 and 83-35         Amounts                Mean Sweat   % Reduction vs.Treatment     Applied (ml)                Output (mg/20 min.)                           N Untreated (95% C.L.)__________________________________________________________________________CPRD 13857 (PG--AlCl)         1.50   148        51                             58.89 (49.62. 66.46)CPRD 13384 (Al:Zr--Gly)         0.50   125        51                             65.35 (57.52. 71.74)Untreated     --     360        68                             0__________________________________________________________________________

Statistical analysis of these combined results indicated that the two treatments do not differ significantly in efficacy at the 0.05 level of significance. It was determined that the compounds do not differ at the 0.10 level of significance, but would differ at 80% confidence (i.e., 0.10<p<0.20).

The conclusion from this Example is that the antiperspirant composition of the present invention is as efficaceous as aluminum--zirconium glycine, the most effective antiperspirant presently known.

Claims (5)

What is claimed is:
1. A method for producing a chemical compound having the formula: ##STR6## where n is an integer from 0 to 1, the unsatisfied valences in the above formula being attached to at least one member of the group consisting of hydrogen atoms, hydroxyl groups, and alkyl radicals containing up to 3 carbon atoms and the linkage --C--(C)n--C-- is a residue of an aliphatic polyhydric alcohol containing from 3 to 6 carbon atoms per molecule which comprises conducting a reaction between aluminum chloride with an aliphatic polyhydric alcohol having from 2 to 6 carbon atoms and having hydroxyl; groups on carbon atoms which are spaced apart by no more than one intervening carbon atom, and subsequently heating the product of said reaction at elevated temperature.
2. The method of claim 1 wherein said subsequent heating is for a time of 24 to 40 hours, at a temperature not greater than about 120° C.
3. The method of claim 1 wherein said reaction is conducted at substantially room temperature.
4. The method of claim 1 wherein the reaction is conducted in the presence of an organic solvent having a dielectric constant from about 2 to about 20 and a boiling point of not greater than about 100° C.
5. The method of claim 1 wherein said product is vacuum dried before said heating at elevated temperature.
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US6083493A (en) * 1999-08-24 2000-07-04 The Procter & Gamble Company Antiperspirant compositions containing isopropyl glycerol ether
US6096298A (en) * 1999-08-24 2000-08-01 The Procter & Gamble Company Deodorant compositions containing isopropyl glycerol ether
US6126928A (en) * 1999-08-24 2000-10-03 The Procter & Gamble Company Compositions containing solubilized, acid-enhanced antiperspirant active
US6149897A (en) * 1999-08-24 2000-11-21 The Procter & Gamble Company Process for making anhydrous compositions containing solubilized, enhanced antiperspirant active
US6399049B1 (en) 1999-08-24 2002-06-04 The Procter & Gamble Company Compositions containing solubilized antiperspirant active
US20090134369A1 (en) * 2007-11-26 2009-05-28 Applied Nanoworks, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof

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US3472929A (en) * 1968-10-23 1969-10-14 Armour Pharma Method of making alcohol-soluble complexes of aluminum
US3792070A (en) * 1971-06-24 1974-02-12 Armour Pharma Basic aluminum bromide-polyol complexes and methods of making same
US3819671A (en) * 1972-10-04 1974-06-25 Oreal Dioxaluminin and dioxaluminane compounds and their preparation
US3956352A (en) * 1973-01-02 1976-05-11 L'oreal Heterocyclic aluminum compounds and process for their preparation

Cited By (12)

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US6083493A (en) * 1999-08-24 2000-07-04 The Procter & Gamble Company Antiperspirant compositions containing isopropyl glycerol ether
US6096298A (en) * 1999-08-24 2000-08-01 The Procter & Gamble Company Deodorant compositions containing isopropyl glycerol ether
US6126928A (en) * 1999-08-24 2000-10-03 The Procter & Gamble Company Compositions containing solubilized, acid-enhanced antiperspirant active
US6149897A (en) * 1999-08-24 2000-11-21 The Procter & Gamble Company Process for making anhydrous compositions containing solubilized, enhanced antiperspirant active
US6399049B1 (en) 1999-08-24 2002-06-04 The Procter & Gamble Company Compositions containing solubilized antiperspirant active
US20090134369A1 (en) * 2007-11-26 2009-05-28 Applied Nanoworks, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof
US20100179339A1 (en) * 2007-11-26 2010-07-15 Auterra, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof
US20100178220A1 (en) * 2007-11-26 2010-07-15 Auterra, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof
US20100178218A1 (en) * 2007-11-26 2010-07-15 Auterra, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof
US8262867B2 (en) 2007-11-26 2012-09-11 Auterra, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof
US8877131B2 (en) 2007-11-26 2014-11-04 Auterra, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof
US9028768B2 (en) 2007-11-26 2015-05-12 Auterra, Inc. Metal alkoxides, apparatus for manufacturing metal alkoxides, related methods and uses thereof

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CA1257603A (en) 1989-07-18 grant
EP0220381A2 (en) 1987-05-06 application
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